1-(1-alkenyl)bicyclo(1.1.0)butanes and their homopolymers

ABSTRACT

DISCLOSED HEREIN ARE BICYCLOBUTANES OF THE FORMULA   1-(R3-C(-R2)=C(-R1)-),2-R7,2-R6,4-R4,4-R5-BICYCLO(1.1.0)-   BUTANE   WHEREIN R1, R2, R3, R4, R5, R6, AND R7 MAY BE HYDROGEN OR A HYDROCARBYL GROUP OF 1-18 CARBON ATOMS WHICH IS FREE OF OLEFINIC OR ACETYLENIC UNSATURATION, WITH THE PROVISCO THAT THE PAIRS R1 AND R2, R2 AND R3, R4 AND R5, AND R6 AND R7 TAKEN TOGETHER MAY, RESPECTIVELY, BE TETRAMETHYLENE OR PENTAMETHYLENE DIRADICALS. THE ABOVE COMPOUNDS ARE PREPARED BY TREATING 3-ALKOXYCYCLOBUTANONE WITH A 1-ALKENYL GRIGNARD REAGENT TO OBTAIN THE CORRESPONDING 1-ALKENYL-3-ALKOXY-1-HYDROXYCLCLOBUTANE WHICH IS TREATED WITH A HYDROGEN HALIDE TO FORM A MIXTURE OF 1-ALKENYL-3-ALKOXY-1-HALOCYCLOBUTANE AND 3-ALKOXY-1-(2HALOALKENYLIDENE) CYCLOBUTANE. THOSE COMPOUNDS ARE THEN TREATED WITH A METAL CAPABLE OF REMOVING HALOGEN (SUCH AS SODIUM, MAGNESIUM, ZINC, ETC.) TO OBTAIN THE CORRESPONDING 1-(1-ALKENYL)BICYCLO(1.1.0)BUTANE. THESE BICYCLOBUTANES CAN BE CONVERTED TO HOMOPOLYMERS, WHICH ARE USEFUL AS SELF-SUPPORTING FILMS, FIBERS AND MOLDING POWDER.

United States Patent US. Cl. 260-666 PY 8 Claims ABSTRACT OF THEDISCLOSURE Disclosed herein are bicyclobutanes of the formula wherein RR R R R R and R may be hydrogen or a hydrocarbyl group of 1-18 carbonatoms which is free of olefinic or acetylenic unsaturation, with theprovisco that the pairs R and R R and R R and R and R and R takentogether may, respectively, be tetramethylene or pentamethylenediradicals. The above compounds are prepared by treating3-alkoxycyclobutanone with a l-alkenyl Grignard reagent to obtain thecorresponding 1-alkenyl-3-alkoxy-l-hydroxycyclobutane which is treatedwith a hydrogen halide to form a mixture of1-alkenyl-3-alkoxy-l-halocyclobutane and 3-alkoxy-l-(2-haloalkenylidene)cyclobutane. Those compounds are then treated with ametal capable of removing halogen (such as sodium, magnesium, zinc,etc.) to obtain the corresponding 1-(1-alkeny1)bicyclo[1.1.0]butane.These bicyclo'butanes can be converted to homopolymers, which are usefulas self-supporting films, fibers and molding powder.

CROSS-REFERENCE TO RELATED APPLICATION This application is a division ofcopending application Ser. No. 6,284, filed on Jan. 27,1970, now US.Pat. No. 3,661,875, issued May 9, 1972.

BACKGROUND OF THE INVENTION Field of the invention This invention isconcerned with a new class of polymerizable organic compounds, and moreparticularly with the 1-(1-alkenyl)bicyclo[l.1.4]butanes and theirhomopolymers.

Description of the prior art New polymerizable monomers with more thanone polymerizable site in a single molecule have long been of interestfor the potential rubbery properties of their polymers and the capacityof the polymers to be cured and crosslinked. The present inventionconcerns a new type of monomer polymerizable at two sites within themolecule and the homopolymers obtained therefrom.

SUMMARY OF THE INVENTION According to the present invention there areprovided 1-(1-alkenyl)bicyclo[1.1.0]butanes of the formula 3,766,282Patented Oct. 16, 1973 ICE in which R R R R R R and K may be hydrogen ora hydrocarbyl group of 1-18 carbon atoms which is free of olefinic oracetylenic unsaturation, with the proviso that the pairs R and R R and RR and R and R and R taken together may, respectively, be tetramethyleneor pentamethylene diradicals (-CH or z)5)- According to the presentinvention there is also provided a process for preparing l-(l-alkenynbicyclo 1.1.01butanes comprising Further, according to the presentinvention the bicyclebutane monomers can be converted to homopolymerswith the aid of free radical, cationic, anionic and coordination-typepolymerization catalysts.

The use of the phrase consisting essentially of does not excludeunspecified conditions or materials which do not prevent the advantagesof the present invention from being realized.

DETAILS OF THE INVENTION The 1-(1-alkenyl)bicyclo[1.1.0]butane monomersof this invention may be represented by the formula in which R R R R R Rand R' are alike or different and may be hydrogen or a hydrocarbyl groupof 1-18 carbon atoms which is free of olefinic or acetylenicunsaturation, with the proviso that the pairs R and R R and R R and Rand R and R taken together may, respectively, be tetramethylene orpentamethylene diradicals ((CH or (CH In defining the terms R to Rabove, the term hydrocarbyl free of ethylenic and acetyleniccarbon-to-carbon unsaturation includes those hydrocarbyl groups which donot contain aliphatic double or triple bonds. Thus, the hydrocarbylgroups as defined herein include alkyl, cycloalkyl, aralkyl, alkaryl,and aryl. Illustrative hydrocarbyl groups as defined hereinabove includealkyl groups, such as methyl, ethyl, t-butyl, hexyl, isooctyl, dodecyl,octadecyl, and the like; cycloal'kyl groups such as cyclopropyl,cyclobutyl, cyclopent'yl, cyclohexyl, cyclooctyl, methylcyclohexyl,3,5-dicyclohexylcyclohexyl, cyclooctadecyl, and the like; aryl groupssuch as phenyl, naphthyl, anthryl, p-phenylphenyl, p-biphenylphenyl,naphthacenyl benzanthryl, chrysenyl, and the like; al-karyl groups suchas p-tolyl, p-cumenyl, 2,4,6-tributylphenyl,. 9,10-diethyll-anthryl,-6-methyl-2-naphthyl, and the like; and aralkyl groups such as benzyl,phenylethyl, diphenylmethyl, a-naphthylethyl, 2-(2-anthryl)ethyl,4-(2,-anthry1)butyl, and the like. Preferred herein are hydrocarbylgroups containing 1-12 carbon atoms, and particularly thosefcontaining1-6 carbon atoms.

' Compounds of Formula I are prepared by the follow ing steps: A3-alkoxycyclobutanone '(II) 'is treated with a l-alkenyl Grignardreagent (III) to obtain the corresponding l-alkenyl-B-alkoxy-lhydroxycyclobutane (IV).

This compound is treated with a hydrogenhalide toform a mixture of al-alkenyl-S-alkoxy-l-halocyclobutane (V) and a3-alkoxy-l-(2-haloalkenylide'ne)cyclobutane (VI). Compound V and/orCompound V1 is then treated'with a metal capable of removing halogen(such as sodium, w magnesium, zinc, or the like) to obtain thecorresponding.

1-( 1-alkenyl)bicyclo[ 1.1.0] butane of Formula I.

This process may be summarized as follows: 7

in which the Rs are defined as above, bromine, or iodine and Y is alower alkyl group, particularly a saturated alkyl group having six orfewer carbon atoms.

The 3-alkoxycyclobutanones of Formula II are ie- 1 pared by the reactionof the appropriate ketene (XV) with the appropriate l-alken'yl ether(XVI) as follows:

metal under anhydrous conditions and in. the presence of an inertorganic solvent such as diethyl ether, dibutyl ether, tetrahydrofuran,and the like. A small amount of a Grignard activating agent may be addedif needed to start the reaction. To the resulting'Grignard solutionisadded gradually the-3-alkoxycyclobutanone of-F0rmula II, the temperaturebeing maintained in the range of 0, to 100 C., and preferably from 0 to50 C. The result ing reaction mixture is treated with aqueous mineralacid.

The organic phase is separated and dried and the1-alk'enyl-3-alkoxy-1-hydroxycyclobutane of Formula IV is re: covered byknown means, such as distillation.

The 1-alkenyl-3-alkoxy-l-hydroxycyclobutane of Fan mula IV is thendissolved in an inert hydrocarbon (pentane, cyclohexane, etc.)-andagitated with a. chemical. excess of concentrated aqueous hydrochloric,hydrobro.

' mic or hydroiodic acid for a period from 1 minute to I so3-alkoxy-l-halocyclobutane of Formula V and3-alkoxy 1 hour or more. Thisreaction is carried out inthe temperature range between 0 C. and 50 C.and preferably at room temperature. The organic phase isthen washed withwater, separated and dried. The resulting l-alkenyl-1-(2-haloalkenylidene)cyclobutane of Formula VI are recovered eitherseparately or as a mixture by known means such as distillation.

The 1-alkeny1-3-alkoxy-l-halocyclobutane of Formula V and/or the3-a1koxy- 1-(2-haloalltenylidene)cyclobutane.

' of Formula VI' are treated with atleast a slight chemical excess of ametalof the type capable of removing halo- X is chlorine,

This reaction is carried out according to the procedure of R. H. Haseket al., J. Org. Chem. 29, 1239-41 (1964).

Compounds of 'Formula II in which any or all oftR'i,

R R and/or R are hydrogen may be furthersubstb, .tuted by treatmentwith. a hydrocarbyl iodide andrsodium- I f hydride to insert thehydrocarbyl groupas R R R 3 and/or R".

The reactionjof a 3-alkoxycyclobutanone of Formula .70

II with a l-alkenyl Grignard reagent of Formula III to form a'3-alkoxy-l-alkenyl-l-hydroxycyclobutane of'Formula IV as shown above ispreferably carried out as folf lows: The Grignard reagent is freshlyprepared by triea'ting the corresponding halide of formula CR R =CR Xwith at least one molecular equivalen of magnesium gen. Suitable metalsare those of Groups I-A, I-B, II-A, and Il-B of the Deming PeriodicTable, e.g., 'Li, Na, K, lRb, Cs, Mg, Ca, Sr, Ba, Cu, Ag, Zn, Cd, Hg,and the likerThe reaction may be carried out mentor in the presence ofan organic'solvent which is inert to the reactants and products.Suitable solvents are hydrocarbons such as pentane and hexane, andetherssuch as diethyl ether and tetrahydroturan. The reaction ispreferably carried out in the temperature range from 0 to C. and mayrequire from a few minutes to several days to yield substantialquantities of the l-(l-alkenyl)bicyclo- [1.1.0] butane monomer ofFormula I. This latter product 'is recovered by known means, such asdistillation. Dur- 'homopolymers by the action'of free radical, anionic,cationic or coordination-type polymerization. catalysts.

The homopolymers of this invention as first formed may contain any orall of the chain units:

- Such units contain catenarian or side-chaindouble bondsor side-chainbicyclo[1-.1.0]butane rings which are sites for further polymerization(i.e., chain branching) or for crosslinking by reaction withcrosslinking agents.

Homopolymers may be represented by a structure having n units ofFormulas VII, VIII and/or IX, where n is greater than 4.

For preparing the homopolymers of this invention, thefree-radical-generating initiators may be selected from a wide varietyof compounds representative of this type of initiator. Included are theazo initiators, e.g., cc,oc'-aZOdiisobutyronitrile, 1,1azodicyclohexanecarbonitrile, dimethyl a,u'-azodiisobutyrate and a,x'-azodiisobutyramide, and the organic peroxides and hydroperoxides,e.g., dibenzoyl peroxide, di-t-butyl peroxide, and t-butylhydroperoxide. The initiators can be used in proportions ranging from0.01 to weight percent of the monomer or comonomers being polymerized.Other sources of free radicals for initiating polymerization may also beused such as electron bombardment, ultraviolet light in the presence ofa sensitizer, and the like.

Suitable solvents and/or dispersion media for freeradical polymerizationinclude water, hydrocarbons such as benzene and hexane, chlorinatedaromatic hydrocarbons such as chlorobenzene, nitriles such asacetonitrile, amides such as dimethylformamide and N-methylpyrrolidone,sulfoxides such as tetramethylenesulfoxide, and the like. It is notessential that a solvent or dispersion medium be used, and bulkpolymerizations can be carried out.

A wide variety of anionic initiators are operable herein forpolymerization. Representative anionic initiators that can be usedinclude the alkali metal alkyls, e.g., n-butyllithium and methyllithium;the alkali metal alkoxides, e.g., potassium t-butoxide and sodiummethoxide; and the alkali metal aryls, e.g., sodium naphthalene. Theconcentration of anionic initiator employed can range from 0.01 to 10weight percent of the monomer or monomers being polymerized. The orderof addition of the monomer and the initiator is not critical.

Suitable reaction media for anionic polymerization include ethers, e.g.,diethyl ether, tetrahydrofuran, and the dimethyl ether of ethyleneglycol; hydrocarbons, e.g., benzene and hexane; chlorinatedhydrocarbons, e.g., chlorobenzene; and amides, e.g., dimethylformamide.The ethers are preferred. However, the polymerization can also becarried out in the absence of solvents.

Representative cationic initiators which may be used include borontrifluoride and trichloride, aluminum trichloride, silicontetrafluoride, phosphorus and arsenic triand pentafluorides andchlorides, aluminum tribromide, titanium tetrachloride, ferric chloride,and the like. The concentration of initiator may be from 0.01 to 10weight percent of the monomer or monomers being polymerized.

Coordination-type initiators usually involve a combination of a lowervalent transition metal chloride with an organometallic compound.Specific combinations which i are useful include diisobutylaluminumchloride with vanadium tris(acetylacetonate), diisobutylaluminumchloride with vanadium oxychloride, triisobutylaluminum with titaniumtetrachloride, methylmagnesium bromide with titanium tetrachloride,lithium aluminumtetradecyl with titanium tetrachloride, and the like.The concentration of initiator may be from 0.01-10 weight percent of themen omer or monomers being polymerized.

Whereas they are not essential, preferred reaction media for carryingout polymerizations initiated by cationictype or coordination-typecatalysts are the hydrocarbons, particularly aliphatic hydrocarbons suchas hexane and cyclohexane and the halogenated hydrocarbons such astetrachloroethylene.

Selection of the particular polymerization initiator is influenced, atleast in part, by the nature of the monomers to be polymerized. Theproper matching of the disclosed monomers and catalysts is well withinthe knowledge of one skilled in the art. Free radical initiators arepreferred.

Selection of the reaction temperature depends largely upon theparticular initiator being used. Some cationic initiators work well atC. Some peroxides work well above 190 C. Generally, a temperature rangeof about C.-200 C. is suitable, however, the full range would not applyto any one of the types of initiators recited. Reaction temperaturesbetween about 20 C. and 60 C. are preferred.

Reaction times can vary from a few seconds, (i.e., 5) to, several days,e.g., 2 to 3 days or more depending on the particular monomers,initiator, solvent, and reaction temperature employed.

Pressures above and below atmospheric pressure are operable. Atmosphericand superatmospheric pressures are preferred.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The examples which follow aremeant to illustrate but not to limit the invention. In the examples, allparts and percentages are by weight unless otherwise specified.

EXAMPLE 1 Part A.--l-hydroxy-1-vinyl-3-ethoxycyclobutane To 14.5 partsof magnesium turnings was added 350 parts of dry tetrahydrofuran and 1part of 1,2-dibromoethane. The solution was heated at 50 C. to activatethe magnesium and then cooled to 25 C. While maintaining the temperatureat 25-35 C., 80 parts of vinyl bromide was bubbled into the solutionover 2 hours. After all the magnesium had dissolved, the solution wascooled. To the solution was added at 0 C. to 10 C. over 1 hour 57 partsof 3-ethoxycyclobutanone in 42 parts of dry tetrahydrofuran. The mixturewas stirred at 25 C. for 1 hour, cooled, and acidified with 50%hydrochloric acid solution. The layers were separated, and 200 parts ofwater were added to the lower water layer. The water was then extractedfive times with 70-part portions of ether, which was then combined withthe original tetrahydrofuran layer. The organic phase was washed with100 parts of saturated sodium bicarbonate solution, 100 parts ofsaturated sodium chloride solution, and then dried over magnesiumsulfate. The solvent was removed, and the residue was distilled to give50 parts of l-hydroxydvinyl-3ethoxycyclobutane, B.P. 46 C./0.35 mm. Theinfrared and NMR spectra were consistent with the proposed structure.

Analysis.Calcd. for C H O (percent): C, 67.57; H, 9.92. Found (percent):C, 66.57, 66.23; H, 10.10, 10.08.

Part B.1-chloro-1-vinyl-3-ethoxycyclobutane and 1-(2- chloroethylidene)-3 -ethoxycyclobutane In a separatory funnel was placed 60 parts ofpentane, 24.6 parts of l-hydroxy-1-vinyl-3-ethoxycyclobutane, and 75parts of concentrated aqueous hydrochloric acid. The mixture was shakenfor 5 minutes, and the layers were separated. The aqueous phase waswashed with 15 parts of pentane and then poured into 300 parts of icewater. This was extracted 3 times with 30-part portions of pentane. Thecombined organic phase was washed four times with ISO-part portions ofice water, 100 parts of saturated sodium chloride solution, and thendried. Removal of solvent and fractional distillation gave 3.7 parts of1- chloro 1-vinyl-3-ethoxycyclobutane, B.P. 43 C./2.7 mm., n =1.4532.

Analysia-C'alcd. for C H OCl (percent): C, 59.82; H, 8.16; Cl, 22.08.Found (percent): C, 59.78; H, 8.36; Cl, 22.29.

The second cut contained 9.3 parts of 1-(2-chloroethylidene) 3ethoxycyclobutane, B.P. 66 C./2.7 mm., n 25=1.4743.

Analysis.-Found (percent): C, 59.52; H, 8.30; Cl. 21.19 (21.92 rerun).

The infrared and NMR spectra were consistent with the proposedstructures.

glass tuberat 60? C. for 2 days. The solid rubbery plug precipitatedzfrom methanol tofgive, crumbs of; tubbery polymer: Ont standing, thepolymer cured and became oxygenof the' air.

filteredofi. 'It was wash'ed thoroughlywith water-and g by the procedurerofrExamplesh Part A, with. Grignard reagents prepared from" thehalidesshown ins I 'dried'to give 1L24g.,of rubbery solid.This'wasdissolved; 1 column B to obtain'the '1-alk'enyl-3alkoxyelhydroxy V .givefOjO g ofsrubbery polym V V lli'artC.-,-1-viny1bicyclobutane V I 1 EXAMPLE A 7 To 30' nartsof magnesium turnings in l000 partso f refiuxing'ether was added over '23hours 161parts of" 1-(2-chloroethylidene)-3-etl1oxycycl0butane. All volatile 7material Was then'i'emoved lilidel 're'duced pressure; Small 1- l V r lamounts of phenothiazine and phenyl-p-naphthylamine' Wlth this. filmCures rapldlyby (Zmsshnkmgto were addedv to the volatiles which werethen distilled; a Stiff selfisuppomng film useful for wrappmgpackagmg aV a and the li'ke. l V 329 24 ,gj ggs fi j i fig iiiggg ia S ggfi gifi}Fibers can be made from the hexane solution by conspec tra wereconsistent with'the proposed structure. l V

s s forrcHs :(percent): C, 89194;TH5, duced areelastielhut afterair-drying they become cross- ;0.06. Found perce butane as described inExample 2 above'can' be made into a clear rubbery'film by casting it ona flat'surface under in hexanesAir drying and erosslinleing usuallytake's'less r V 7 7 1 can be molded, for example, into durablecontainers 'ofi flomopplymerpf b YE b 7 j mzs varioussi zes anddescriptions, s r VA sample of l-vinylbicyclobutzinecontaining, a smallamount of a,a-az'odiisobutyronitrile was heated; in a sealedv v wasremoved from' the, tube, dissolved in hexane, and pressure followed bydryingiand m g EXAMPLEaB'IJ I 1- a harder presumably through i ii l l mlm l lbicyclobutane vas described in Example 3, is suitable for'EX'AMP'LE:

o V V V scribed infExampleAabove. e

In a'jgla'ss reactor and 'under'a nitrogen: atmosiihere'; 5 7 Di cu siof the: t bl 7 mixture of 1.6ml. o f I-VmylbwyClObutane, 0-10 7 Otherl-(1-alkenyl)bicyclofLlfl'lbutanesare prepared a:azodnsobntyronitnle, 10ml.4o-f--l0% aqueouszsoap;

" solution andioi'mLsofisobutyraldehvdeiwas agitatedQatil h n A"'and lkl ethersfshe'wniin ig nn i C- @9 hoursw l m mtrolgen substituted inztheprocedures of; Haseket all noted above actlon' mlxtur? W h f i /Q toobtain the 3-alkoxycyclobutanones of Formula, II 'q Kcl and, the'Coagulated Solid 'P Y Q shown in column C. These latter compoundsar'ethen in chlor oform to'yield a polymer "solution suitablefor,filmcasting; etc, see Example B be'lows The po'lymerlwa'cyclob'utanes of Formula IV shownin eolumnhEi Theserrecoveredifrom"chloroformsvlufionby drowlgiinigi turn are substitutedfor3-ethDxy*I-hydroxy-l-vinyh v 93 95 m r e q oyclobutane in thelprjoeedures ofExamp/l'el, Bartel}, and 7 terrthlsywavs Q' to" obtainthe l -(balkehYlibiGtlclot-LLOJbntanes-Vof.

anol. It wasffiltered, still Qnnder to air for a few hours it was nolonger soluble in chloro g Formula I Shown in o s F These, 1 alkcnnynbkr form l-for'durablecups,"!boxesand' containers of various descriptions.l

v s V by employing the procedunes oii Examples 2 and 3 ZISWBH V I j 7 5-as the other initiating systems described above; 7

The homopolymersof this invention are useful m'the Ethyl l3oct.adecy1viny1 ether use in item 14 f h A ffreslily prepared hexanesolution of l-vinylbievclo- V Y a: doctor blade and evaporating thehexane; ,Up'on con: 7 7' ventional dry spinning techniques Theffi bersinitially pr0- m); c 88.82" 88175" H 9.32 10502;; linkfldrandr become si a strong andno l -se u l EXAMPIJE'ZZ "than l2-hours. Fibers canhoused: in wearing apparel rori One method'ior molding is to paele'thesolvent-damp and not yet completely crosslinked fibers (or crumbs,=apieces etc.) intolsuitablemolds'of thedesired shapes" e 25 orming film,fibers andlmolded articles ge as dc as summarizedlin theitablebelowl'Known ketenewshownf V form of PP ting'film f PP P fickagivllgilgI 1 table 'is prepared by treatingeieosanal with ethanolin: in t e formof fibers 0 clothlng fabrics; and 1H d l ,the presence of an acidiccatalyst to obtainthe correspond- Ting diethyl acetal. Theacetalis'treated'with a strong acid :5 to split out ethanol and yieldethyl floctadeeylvinyl ether.

- 7 V TABLE Item tAsKe tene v V I I V B. l-AlkenylEther, V I v I C.3-Alkoweyelobutanonel- 1 H CHgCl L GHQ-CH3 I I -l a e I) HaC-H2G G'HPHGICH: v

:1 V l I 10 TABLEComtlnuefl B. l-Alkenyl Ether C. 3-A1koxycyc1obutanoneItem A. Ketene m C P Q m m "w 0 "w "PH. 0 0 0 c VAC 0 H 0 KB H w w m m Hw H H 4 H H H w m H H 4 H H r C 0 P M r a m 3 H a H. )H "M w H "V. H H HH h. \CHC H 0 /C H/ \o mu m H G H H H CH0 m w H H H H O;3-A1koxycy1obutanone' Item A. Ktne II v Hzi-GH:

ltein D. Halide 0:63: V 6 HI 0 H3 0 ion- 0m 3,766,282 1 TABLE-Continued1m D. Halide E. l-alkenyl-3 21lkoxy-l-hydroxycyelobutano 12 701 v I VH2O 0H: on 7 Bio H: H2O 31121 H\, OH H20CH 2 1530-0 0:01; Hzci C 7 moon, t 112 1- 6 a I w Hie-on, 13... 1

14..." 1'31 mHm) ieHa7) H OH (Cia a1) H,c-H2oo x a m- 0mm V H CeHafi lwl-I51) t I V H H o=o--cn= H OH I I-o- The embodiments of the inventionin' which anexclunes in "which, R7 R R ,,R R5 R. iand R", are selectedfrom the group consisting of hydrogen or a hydrocarbyl group of 1-18carbon atoms which is free of olefinic or acetylenic unsaturation, withthe proviso that the pairs R and R R and R R and R and R and R takensive property or privilege is claimed are defined as follows:

1. 1-(1-alkenyl)bicyc1o[1.1.0]butanes of the formula tQ-HQCXCHP e HCiwQwH, H3C-HzC-O o=oom x V a o Hz 7 Ha C Hi 7 H:

70 together may, respectively, be tetramethylene or penta- C methylenediradicals [--(CH or (CH V 2. The compounds of claim 1 in which thehydrocarbyl i l 7 groups contain 1-12 carbon atoms. 3. The compounds ofclaim 2 in which the hydrocarbyl r 75 groups contain 1-6 carbon atoms.

4. The compounds of claim 1 in which the hydrocarbyl groups are selectedfrom the group consisting of methyl, ethyl, t-butyl, hexyl, isooctyl,dodecyl, octadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexylcyclooctyl, methylcyclohexyl, 3,S-dicyclohexylcyclohexyl,cyclooctadecyl, phenyl, naphthyl, anthryl, p-phenylphenyl,p-biphenylphenyl, naphthacenyl, benzanthryl, chrysenyl, p-tolyl,p-curnenyl, 2,4,6-tributylphenyl, 9,l-diethyl1- anthryl,6-methyl-2-naphthyl, benzyl, phenylethyl, diphenylmethyl,a-naphthylethyl, 2-(2-anthryl)ethyl, or 4- (2-anthryl)butyl.

5. The compound of claim 1 in which R R R R R R and R' are hydrogen;l-vinylbicyclobutane.

6. A process for preparing the 1-(1-alkenyl)-bicyclo- [1.1.0]butanes ofclaim 1 comprising:

(1) contacting 3-alkoxycyclobutanone with a l-alkenyl Grignard reagentunder anhydrous conditions while dissolved in an inert organic solventat about 0 C. 100 C. and adding aqueous mineral acid to the resultingreaction mixture to obtain the corresponding1-alkenyl-3-alkoxy-l-hydroxycyclobutane;

(2) contacting said l-alkenyl 3 alkoxy 1 hydroxycyclobutane in an inerthydrocarbon solvent with an aqueous hydrogen halides selected from thegroup consisting of hydrogen chloride, hydrogen bromide and hydrogeniodide, at about 0 C.50 C. to form a mixture of1-alkenyl-3-alkoxy-l-halocyclobutane 8 and 3-alkoxy-l (2haloalkenylidene)cyclobutane; and

(3) contacting said 1-alkenyl-3-alkoxy 1 halocyclobutane and/ or 3alkoxy 1 (2 haloalkenylidene) cyclobutane at about 0 C.-100 C. with ametal capable of removing halogen to obtain the corresponding 1-1-alkenyl)bicyclo 1.1.0] butane.

7. The process of claim 6 wherein the 3-alkoxycyclobutanone is contactedwith the l-alkenyl Grignard reagent at about 0 C. C.

8. The process of claim 6 wherein the 1-alkenyl-3-alkoxy-l-hydroxycyclobutane is contacted with an excess of hydrogenhalide at room temperature.

References Cited UNITED STATES PATENTS 3,383,371 5/1968 Natta 260-79.53,520,941 7/1970 Rifi 260-666 Py 3,523,928 8/1970 Blanchard 260- DELBERTE. GANTZ, Primary Examiner V. OKEEFE, Assistant Examiner US. Cl. X.R.26085.5, 93.1

mg UNITED STATES PATENT OFFICE CERTIFICATE (3F CORRECTION Patent No.'3:,7 ,282 Dated October 16, 1963 Inventor) James B. Seija It iscertified that error appears in the above-identifiezd patent and thatsaid Letters Patent are hereby corrected as shown below:

Col. 1, line 51 "l.l, should be "1.1.0". Col. 3, line 36, formula v "R8"end "R6" should be "R6" and "R7", I

0010 6, line 6 5- insert hyphen after "chloro".

' CH3 CH3 II 1| ll 1! C01. 100, item 6 ,H3C-\ should be v HSC- v H3CCol. 95, item 12 "H C-O" should be "s c-o". C01. 120, item-1 L"(C16H37)" should be Re u (three occurrences) Col. 13D, item 10 A:should be H3- CH2- s c-- css H2C--CH2 col 1313, item 11 =0 should be =0l H2C-CH2 H2C'-CH2 001s, 15-16, E 84: F, item 1 "(0 537) should he "(0811 7) (l0 occurrences).

col. 1?, line 2M "halides" should be "halide".

Signed and sealed this 9th day of April 1971 (S Attest:

EDWARD FLFLETCHERJR. C; MARSHALL DANN Attesting Officer Commissioner ofPatents

